Indigoid vat-dyestuffs and process of making same



Patented Feb. 20, 1934 PATENT OFFICE INDIGOID VAT-DYESTUFFS AND PROCESSOF MAKHNG SAME Jakob Miiller, Munchenstein, near Basel, and

Robert Stoclrer, Basel,

Switzerland, assignors to firm: Society of Chemical Industry in Basie,

Basel, Switzerland No Drawing. Application August 3, 1931, Serial No.554,940, and in Switzerland August 8, 1930 18 Claims.

The present invention relates to the manufacture of indigoidvat-dyestufis. It comprises the process of making these dyestuffs, aswell as the dyestuffs themselves.

According to this invention, new unsymmetrical indigoid dyestuffs aremade by condensing a body of the general formula:

(wherein one :1: represents alkyl, the other a: halogen and y a reactivegroup, such as O, anil, 2H, NOH, halogen) with a compound of the generalformula (wherein 2 represents a reactive group, such as O, halogen, ai2H, NOI-I, and wherein V, W and represent atoms 01" which two are carbonatoms adjacent to each other and at the same time appertaining to anaromatic ring system, and the third is NH, C or S), in which twoformulae the groupings and must be present in among themselves differentstages of oxidation.

Compounds of the first named formula are, for instance,5-ch1oro-6-methyl-3-hydroxythionaphthene,5-chloro-6-ethyl-3-hydroxythionaphthene,5-bromo-6-n1ethyl-3-hydroxythionaphthene, 5- methyl-G-chioro-S-hydroxythionaphthene, 5 1nethylS-brorno3-hydroxythionaphthene, the 2-anil and the para-dimethylamino-2-anil of these bodies (which areobtainable for example by condensing the 3-hydroxythionaphthene with anromatic nitroso-compound) the thionaphthenequinones corresponding withthe said 3-hydroXythionaphthenes (obtainable, for example, by treatingthe 2-anils with a saponifying agent, such as sulfuric acid), thecorresponding thicnaphthenequinone-Z-monoor 'Z-dihalides (obtainable forexample from the 3-hydroxythionaphthenes by action of halogen or agentsyielding halogen), and the thionaphthenequinoneoximes.

From the 3-hydroxythionaphthenes which are substituted in 5- and(i-position by halogen and alkyl, the 5-aliyl-6-halogen3-hydroxythionaphthene can for example be made in thefollowing manner l-alkyl-2-haiogen-e-benzene-sulfochloride is reduced,the l-alkyl-2-halogen-4-thiophenol thus produced condensed in a weaklyalkaline solution with monohalogen acetic acid, and thel-alkyl-2-halogen-e-phenyithiogiycollic acid obtained converted into the5-alky1-6-halogen-3-hydroxythionaphthene either by the action of agentswhich eliminate water, such as, for example, sulfuric acid,chloro-sulionic acid, or, by conversion into the l-alkyl-2-halogen-4-phenylthioglycollic acid chloride by means of phosphorus trichloride,and acting thereon with agents which inate hydrochloric acid, such asaluminium chloride.

The 5-halogen-6-alkyl-3-hydroxythionaphthenes and also the 2-carboxylicacids thereof may be made for example by the following meth od: 5-alkyl-4-halogen-Z-arninobenzene 1 -sulionic acids are diazotized andconverted by means of cuprous cyanide into the 5-alkyl-4-halogen-2cyano-l-benzenesulfonic acids; by the action of phosphorus pentachlorideon the latter body the corresponding sulfochlorides are formed. Theseare reduced by means of zink dust to the thiophenol carboxylic acids, orthe amides thereof and saponified, and the latter are condensed withmonohalogen acetic acid to form the 5-alkyl-4- halogen- 1phenyl-thioglycol-2-carboxylic acids. By heating these carboxylic acidswith alkalies there are obtained the corresponding 5-halogen-6-alky1-3-hydroxythionaphthenes or their 2- carboxylic acids.

Bodies of the second named formula are, for instance, five-memberedcondensed ring systems, as for example isatins, naphthisatins, indoxyls,thionaphthenequinones, hydroxythionaphthenes, naphthoh droxythiophenes,acenaphthenequinones and the like, their homologues and substitutionproducts, anii and halides.

The condensation takes place by heating the components in a solventwhich may act as condensing agent.

The dyestuffs thus obtained correspond with the general formula C C-Vwherein the :rs, r, V and W have the signification as hereinbeforedefined. They form orange to red, violet, brown to black-grey powders,which dissolve in concentrated sulfuric acid to violet, brown and greensolutions, yielding with hydrosulfite and caustic soda solution yellow,orange, violet and greenish black vats, which dye= cotton fast scarletto red, violet, brown and grey tints.

These dyestufis may further be converted into dyestuffs containing morehalogen by subsequent halogenation.

The dyestuffs corresponding to the above general formula arecharacterized by a surprising beauty, high coloring power and very goodprop erties of fastness. Particularly valuable products are obtained bycondensing the B-hydroxythionaphthenes substituted in 5- and 6-positionby halogen and methyl, or their reactive 2-darivatives, withnaphthohydroxythiophenes or their reactive 2-derivatives.

The new dyestufis may be converted into their leuco ester salts in theknown manner.

The following examples illustrate the invention, the parts being byweight:

Example 1 198 parts of 5-methyl-6-chloro-3-hydroxythionaphthene and 182parts of acenaphthenequinone are suspended in 4000 parts of alcohol andthe suspension is heated to boiling. When condensation is finished thedyestuif of the formula 0 ll CH3 o=o-o=o which separates in good yieldis filtered, washed and dried. It is a scarlet red powder, soluble insulfuric acid to a green solution. The dyestuff forms a blue-violet vatand dyes cotton strong scarlet tints of characteristic fastness tochlorine and bowking.

The corresponding dyestuif from 5-methyl-6- bromo-B-hydroxythionaphthenedyes somewhat more yellow tints.

Example 2 Example 3 330 parts of para-dimethylaminoanil of 5-methyl-6-chlor0-3 hydroxythionaphthene and 198 parts ofl-methyl-G-chloro3-hydroxytl'iionaphthene are suspended in 4000 parts ofbenzene and the suspension is heated to boiling; after the boiling hascontinued for a short time the condensation is complete. The newdyestuff of the formula is a bright red powder, soluble in sulfuric acidto a green solution. Its yellow vat dyes cotton strong bluish-rose tintsof very good fastness to chlorine and bowking.

Instead of the paradimethylaminoanil there may be used with similarresult the 5-methyl-6- chloro-3-hydroxythionaphthenequinone.

Example 4 330 parts of para-dimethylaminoanil of 5- methyl-G-chloro-Bhydroxythionaphthene and 200 parts of 2zl-naphthoxythiophene aresuspended in 4000 parts of alcohol and the suspension is heated toboiling until the condensation of the dyestufi is complete. The whole isfiltered and the dyestuff of the formula dried. It is a bordeaux redpowder and dyes cotton in an orange vat yellowish bordeaux tints, veryfast to chlorine, bowking and light.

Example 5 305 parts of 5:7-dibrornisatin are suspended in is obtained inthe form of a red-violet powder which dissolves in sulfuric acid to abluish-green solution.

It forms a yellow vat and dyes cotton strong reddish violet tints ofgood properties of fastness.

Example 6 385 parts of the dyestuif made as described in Example 5 areintroduced into 6000 parts of hitrobenzene and the whole is mixed with180 parts of bromine. The mixture is heated in the course of 72 hours at160 C. The dyestuif is separated by filtering, washing with alcohol anddrying. The brorninated dyestuff is a blue violet powder soluble insulfuric acid to a blue-green solution.

It yields a yellow vat and dyes cotton bluish violet tints.

its

Example 7 198 parts of 5-chloro-6-methyl-3-hydroxythionaphthene and 330parts of para-dimethylto dyestuff is finished. The new dyestuff of theformula aminoanil of 5-chloro-'7-methyl-3-hydroxythio- 8t naphthene aresuspended in 4000 parts of alcohol and the suspension is heated toboiling. After CH? boiling for a short time the condensation is coms Splete. The new dyestuff of the formula 0 0 thus obtained is filtered anddried. It is a brown 1 powder which dyes cotton in an orange vat strong01 yellowish bordeaux tints of very good fastness to 0:0 chlorine,washing and bowking. CH? Example 10 374.5 parts ofpara-dimethylaminoanil of 5- 0H1 methyl-G-bromo 3 hydroxythionaphtheneand 234.5 parts of l-chloro-Z:3-naphthoxythiophene is a violet redpowder, soluble in sulfuric acid to g: idspendgd i 3 g i q fi a the areen solution. Its yellow vat dyes cotton n-swn lsnea e 01mg un 1 6condensation to tne dyestuff is complete. The whole strong ofpfiqnounced fastness is then filtered, washed with alcohol and dried. tochlorine, washing and bowmng. The new dyestuff of the formula 7 Example8 (If 0 m0 243 parts of 5-bromo-6-methyl-3-hydroxythio- CH II naphtheneand 182 parts of acenaphthene-quin- 3- one are suspended in 4000 partsof alcohol and Cl \S the suspension is heated to boiling. Whencondensation is complete the dyestufi of the formula is a red-violetpowder which is soluble in sul- O furic acid to a green solution. Ityields a yellow l vat from which cotton is dyed strong violet tints Brofvery good fastness to light, chlorine, washing 111g) C=CC=O andKeir-boiling. on Example 11 5 parts of the dyestuff obtained asdescribed in Example 5 aremade into a paste with 20 parts of causticsoda solution of 33 per cent. strength. 750 parts of water of 70 C. areadded, together with 15 parts of sodium hydrosulfite. The whole which isformed in good yield, is filtered, washed is allOWed Stand for 30 mnutes, and then diand dried. It is a scarlet red powder soluble in Wit-hWater t0 2900 P 100 P ts of Octsulfuric acid to a green solution. Itform a ton are entered at 60 C. and after about 10 lack-violet vat whichdyes cotton strong yelminutes 50 parts of mmon salt are added andlowish-scarlet tints of pronounced fastness to the dyeing is continued-/2 hour at 60 C. chlorine, washing nd hawking, The goods are thenremoved from the bath, oxidized in air for hour, "ins-ed and soaped. TheExample 9 cotton is dyed reddish violet shades. For W001, 330 parts ofpara-dimethylaminoanil of 5- Si a d a ficia S k t e dyeing process mustchloro-B-methyl 3 -hydroxythionaphthene and Obv o sly be va ied to Suitthe material. 200 parts of 2:1-naphthoxythiophene are sus- In the wi gtable, further examp OI pended in 4000 parts of alcohol and thesuspendyestuffs obtainable according to this invention sion is heated toboiling until the condensation are set forth: 13o

5-inethyl-6-ch1oro-3-hydroxythionaphthene and: g g fg 3135 252 C0125;the gig tton I. a-isatin anilide Heliotrope Green... Yellow Heliotrope.

II. 5:7-dibromisatin-chlor d Red violet- Green... ellow Violet.

III. 5:7-dibromisatin Red Red-brown... Golden-yellow Red-brown.

IV. Para-dimethylaminoanil 0123 ydro yth naphthena... Bordeaux red.Green Yellow Red.

V. Pora dimethylaminoanil of 5 chloro-7-methyl-3-hydroxythio- Bluish-redGreen Yellow Bluish-red. VI.P. d i r n ?hylaminoanil of6-ethoxy-S-hydroxythionaph- Bordeaux red. Violet. Yellow Bluish-red. 1A6VII. Parefdi rnethylaminounil ol lz2-naphthoxythiophene Bordeaux red.Dark olive Orange Bluisli bordeaux.

VIII. Para-dimethylaminoanil of 2:3-naphthoxythiophene Violet Olivegreen... Orange Blue violet.

IX. Para-dimethylaminoanil ofl-chloro-2:3-naphthoxythiophene Red violetGreen Yellow Violet.

X. wisatin anilide-.. Dark violet... Olive greed... Yellow Violet.

XI. 5-bromo-a-isatin-chloridc Dark violet.-. Blue green G 120? 11 i s hBlue-grey.

XII. Para-dimethylaminoanilof6-chloro-3-hydroxythionaphtheue.. Bordeauxred. Green Yellow. Ligliit bordeaux g5 XIII. Para-dimethylaminoanil of4-methyl-6-chloro-3-hydroxythio- Violettish red. Green Yellow Violettish red.

XIV. eiiiigr g i een Red brown Brown Yellow Red.

XV. Para-dimethylaminoanil of lz2-naphthoxythiophene Rbcr (:1 W31 i s hOlive green Orange Bordeaux red.

XVI. Para-dimethylaminoanilof2:3-naphthoxythiophene Blackisli grey.Green Yellow Grey. 5

The dyestuif No. I. corresponds with the formula The dyestufi No. IIIcorresponds with the formula if I? o o CHa- M NH The dyestuff No. VIcorresponds with the formula 0 o t t CH The dyestuff No. XII correspondswith the formula 0 o t t o=o om- 01 The dyestuff No. XVI correspondswith the formula What we claim isz- 1. Process for the production ofunsymmetrical indigoid dyestuffs, consisting in condensing bodies of thegeneral formula wherein one 2: stands for methyl and the other a: forchlorine, with products having the general formula wherein V, W and 1*represent atoms of which two are carbon atoms adjacent to each other andat the same time appertaining to an aromatic ring system, and the thirdis NH, C, or S.

2. Process for the production of unsymmetrical indigoid dyestuffs,consisting in condensing bodies of the general formula wherein one :0stands for methyl and the other :1 for chlorine, with products havingthe general formula wherein V, W and r represent atoms of which two arecarbon atoms adjacent to each other and at the same time appertaining toan aromatic ring system of the naphthalene series, and the third is NH,C, or S.

3. Process for the production of unsymmetrical indigoid dyestuffs,consisting in condensing bodies of the formula O=anil Gilac withproducts having the general formula wherein V, W and r represent atomsof which two are carbon atoms adjacent to each other and at the sametime appertaining to an aromatic ring system of the naphthalene series,and the third is NH, C, or S.

4. Process for the production of unsymmetrical indigoid dyestuffs,consisting in condensing bodies of the formula g 0 CH C=anil Br \S withproducts having the general formula VC=O i i/ W o wherein V, W and 7"represent atoms of which two are carbon atoms adjacent to each other andat the same time appertaining to an aromatic ring system of thenaphthalene series, and the third is NH, O, or S.

5. Process for the production of unsymmetrical indigoid dyestuffs,consisting in condensing bodies of the formula wherein T represents S orNH, and in which the two carbon atoms C1 and C2 appertain to an arcmaticring system of the naphthalene series.

6. Process for the production of unsymmetrical in which the two carbonatoms C1 and C2 appertain to an aromatic ring system of the naphthaleneseries.

'7. Process for the production of unsymmetrical indigoid dyestuffs,consisting in condensing the body of the formula with a product of theformula 8. Process for the production of unsymmetrical indigoiddyestuffs, consisting in condensing the body of the formula with aproduct of the formula 9. The unsymmetrical indigoid dyestuffs of thegeneral formula wherein one x stands for an alkyl radical of the loweraliphatic series, the other x for halogen, and 1', W and V representatoms of which two i are carbon atoms adjacent to each other and at thesame time appertaining to an aromatic ring system, and the third is NH,S or C, which products form orange to red, violet, brown to black greypowders, which dissolve in concentrated sulfuric acid to violet, brownand green solutions, yielding with hydrosulfite and caustic sodasolution yellow, orange, violet and greenish black vats from whichcotton is dyed fast scarlet to red, violet, brown and grey tints.

10. The unsymmetrical indigoid dyestufis of the general formula whereinone it stands for an alkyl radical of the lower aliphatic series, theother a: for halogen, and r, W and V represent atoms of which two arecarbon atoms adjacent to each other and at the same time appertaining toan aromatic ring system of the naphthalene series, and the third is NH,S or C, which products form red, violet, brown to black grey powders,which dissolve in concentrated sulfuric acid to green solutions,yielding with hydrosulfite and caustic soda solution yellow, orange,violet and greenish black vats from which cotton is dyed fast scarlet tored, violet and grey tints.

11. The unsymmetrical indigoid dyestuffs o the general formula whereinone a 'stands'for methyl, the other a:

for chlorine, and r, W and V represent atoms of which two are carbonatoms adjacent to each other and at the same time appertaining to anaromatic ring system of the naphthalene series, and the third is NH, Sor C, which products form red, violet, brown to black grey powders,which dissolve in concentrated sulfuric acid to green solutions,yielding with hydrosulfite and caustic soda solution yello v orange,violet and greenish black vats from which cotton is dyed fast scarlet tored, violet and grey tints.

12. The unsymmetrical indigoid dyestuffs of the general formula whereinone 0: stands ior'methyl, the other a: for chlorine, and 1' represents Sor NH, and in which the two carbon atoms C1 and C2 appertain to anaromatic ring system of the naphthalene series, which products form red,violet, brown to black-grey powders, which dissolve in concentratedsulfuric acid to green solutions, yielding with hydrosulfite and causticsoda solution yellow, orange, violet and greenish-black vats from whichcotton is dyed fast scarlet to red, violet and grey tints.

13. The unsymmetrical indigoid dyestuffs of the general formula 0 o 2',u C-C1 W I Z- \S/ S-Cz wherein one 3: stands for methyl and the other a:for chlorine, and in which the two carbon atoms C1 and C2 appertain toan aromatic ring system of the naphthalene series, which products formred, violet, brown to black-grey powders, which dissolve in concentratedsulfuric acid to green solutions, yielding with hydrosulfite and causticsoda solution yellow, orange, violet and greenishblack vats from whichcotton is dyed fast scarlet to red, violet and grey tints.

14. The unsymmetrical indigoid dyestuffs of the general formula whereinthe two carbon atoms C1 and C2 appertain to an aromatic ring system ofthe naphthalene series, which products form red, violet, brown toblack-grey powders, which dissolve in concentrated sulfuric acid togreen solutions, yielding with hydrosulfite and caustic soda solutionyellow, orange, violet and greenish-black vats from which cotton is dyedfast scarlet to red, violet and grey tints.

16. The unsymmetrical indigoid dyestuffs of the general formula whereinthe two carbon atoms C1 and C2 appertain to an aromatic ring system ofthe naphthalene series, which products form red, violet, brown toblack-grey powders, which dissolve in concentrated sulfuric acid togreen solutions, yielding with hydrosulfite and caustic soda solutionyellow, orange, violet and greenish-black vats from which cotton is dyedfast scarlet to red, violet and grey tints.

17. The unsymmetrical indigoid dyestuff of the formula which productforms a bordeaux powder, which dissolves in concentrated sulfuric acidto a green solution, yielding with hydrosulfite and caustic sodasolution an orange vat from which cotton is dyed fast yellowish bordeauxtints.

18. The unsymmetrical indigoid dyestufi of the formula which productforms a red violet powder, which dissolves in concentrated sulfuric acidto a green solution, yielding with hydrosulfite and caustic sodasolution a yellow vat from which cotton is dyed fast violet tints.

JAKOB MiiILER. ROBERT STOCKER.

